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Strawberry tree honey is a high-value honey from the Mediterranean area and it is characterised by a typical bitter taste. To possibly identify the secondary metabolites responsible for the bitter taste, the honey was fractionated on a C18 column and the individual fractions were subjected to sensory analysis and then analysed by liquid chromatography coupled with high-resolution tandem mass spectrometry in negative ion mode, using a mass spectrometer with an electrospray source coupled to a hybrid high resolution mass analyser (LC-ESI/LTQ-Orbitrap-MS). A chemometric model obtained by preliminary principal component analysis (PCA) of LC-ESI/LTQ-Orbitrap-MS data allowed the identification of the fractions that caused the perception of bitterness. Subsequently, a partial least squares (PLS) regression model was built. The studies carried out with multivariate analysis showed that unedone (2-(1,2-dihydroxypropyl)-4,4,8-trimethyl-1-oxaspiro [2.5] oct-7-en-6-one) can be considered responsible for the bitter taste of strawberry tree honey. Confirmation of the bitter taste of unedone was obtained by sensory evaluation of a pure standard, allowing it to be added to the list of natural compounds responsible for giving the sensation of bitterness to humans.

In recent years, the use of organic substances has been increased to improve the production of specialized metabolites in aromatic and medicinal plants. Salvia officinalis L., known as sage, is an important medicinal and aromatic plant, whose leaves are commonly used as a condiment in food but mainly as a raw material in pharmaceutical and perfumery industries. In this work to define the effects of bio-fertilizers and foliar applications of l-phenylalanine on specialized metabolites production and biochemical characteristics of S. officinalis leaves, an experimental field in 2 years (2016 and 2017) was developed in semiarid climate, South-western, Iran. Experimental treatments included foliar spraying of l-phenylalanine in diverse concentration (0-250 and 500 mg/mL) and different bio-fertilizers [Arbuscular mycorrhizal fungi (AMF), Pseudomonas fluorescens (Pf), both fungi and bacteria (AMF + Pf)]. A metabolomics approach was carried out on the ethanolic extracts of sage leaves obtained by different treatments using Liquid Chromatography coupled with High-Resolution Mass Spectrometry (LC-ESI/LTQ-Orbitrap/MS) followed by multivariate data analysis. A total of 41 specialized metabolites were detected, and 35 of them were identified based on their accurate mass and mass fragmentation, as belonging to organic acids, phenylpropanoids, flavonoids, diterpenes, salvianolic acids and oxylipins. This work highlighted that the foliar application of l-phenylalanine along with the inoculation of Arbuscular mycorrhizal fungi and P. fluorescens can improve the yields of specific metabolites of pharmaceutical interest.

Liquid preparations such as tinctures and infusion derived from Ribes nigrum L. (black currant) leaves are widely used in Europe. Despite the various uses reported for the infusion and hydroalcoholic extracts of the leaves of this species, their chemical profile has not yet been defined. In the present study, the infusion, hydroalcholic and methanolic extracts prepared from R. nigrum leaves were analyzed. LC–MS analyses of these extracts allowed the characterization of 31 phenolic compounds mainly belonging to organic acids, flavonoids, catechins and its oligomers. Quantitative results proved that these preparations are a rich source of polyphenols and flavonoids and among them the infusion presented the highest polyphenol levels. A metabolomics approach was also used for the comparison and evaluation of the chemical composition of the different extracts obtained from R. nigrum leaves.

Psoriasis is an inflammatory disease of the epidermis based on an immunological mechanism involving Langerhans cells and T lymphocytes that produce pro-inflammatory cytokines. Genetic factors, environmental factors, and improper nutrition are considered triggers of the disease. Numerous studies have reported that in a high number of patients, psoriasis is associated with obesity. Excess adipose tissue, typical of obesity, causes a systemic inflammatory status coming from the inflammatory active adipose tissue; therefore, weight reduction is a strategy to fight this pro-inflammatory state. This study aimed to evaluate how a nutritional regimen based on a ketogenic diet influenced the clinical parameters, metabolic profile, and inflammatory state of psoriasis patients. To this end, 30 psoriasis patients were subjected to a ketogenic nutritional regimen and monitored for 4 weeks by evaluating the clinical data, biochemical and clinical parameters, NMR metabolomic profile, and IL-2, IL-1β, TNF-α, IFN-γ, and IL-4 concentrations before and after the nutritional regimen. Our data show that a low-calorie ketogenic diet can be considered a successful strategy and therapeutic option to gain an improvement in psoriasis-related dysmetabolism, with significant correction of the full metabolic and inflammatory status.

The research aimed to evaluate the polyphenolic composition and the antioxidant capacity of edible extracts of feijoa (Acca sellowiana (O. Berg) Burret) flowers. Phenolic compounds of whole feijoa flower (FM), feijoa petals (PM) and feijoa petals juice (PJ) were identified by high-performance liquid chromatography coupled with electrospray mass spectrometry and quantified by liquid chromatography coupled with ultraviolet/visible detection. Moreover, the total polyphenol (TP) content was measured spectrophotometrically and the antioxidant capacities of the extracts were evaluated by FRAP, CUPRAC, DPPH(·), and ABTS(·+) assays. The FM showed TP content (395.14 ± 7.91 mg GAE/L) higher than PM and PJ, and exhibited better antioxidant capacities. FM extracts were characterized by the high content of anthocyanins (115.3 ± 3.6 mg/L), flavonols (42.9 ± 3.3 mg/L) and the presence of ellagic acid (7.9 ± 0.2 mg/L) and other galloyltannins. In addition, cyanidin-3-O-glucoside and apigenin were detected in all the three extracts. The present study provided an overview on particular bioactive compounds that characterise different parts of edible feijoa flowers. Among the latter, FM proved to be the most suitable for exploitation in the food and health manufactory. GRAPHIC ABSTRACT: [Image: see text]

Cancers affecting the salivary glands have been an increasing incidence. Salivary gland cancer is not detected until it reaches an advanced stage, which would generally result in a poor prognosis and survival rate. Therefore, early detection as well as the screening of high risk populations with precancerous lesions remains an unmet medical need. In the present work, we present a NMR-based metabolomic study of the saliva of patients suffering from salivary gland tumours. Analysis of data was done using a combined approach based on PRICONA quantitative analysis and statistical multivariate analysis. Interestingly, both the analytical methods indicate that individuals affected by parotid tumour have a characteristic metabolomic profile characterized by abnormalities in the concentration of several aminoacids. Among these the most significant are those relative to Alanine and Leucine suggestive of an alteration in the metabolic pathways of glycogenic aminoacids and ketone bodies. Our data, describing the preliminary metabolomics fingerprint of parotid tumour, are consistent with the recent view that oncogenic signalling corresponds to alteration in the metabolism of nutrient pull (Vander Heiden et al., 2009), rather than to a single metabolite.

Corylus avellana L. (Betulaceae) leaves, consumed as infusion, are used in traditional medicine, for the treatment of hemorrhoids, varicose veins, phlebitis, and edema due to their astringent, vasoprotective, and antiedema properties. In previous works we reported from the leaves of Corylus avellana cv. "Tonda di Giffoni" diarylheptanoid derivatives, a class of plant secondary metabolites with a wide variety of bioactivities. With the aim to give an interesting and economically feasible opportunity to C. avellana leaves as source of functional ingredients for pharmaceutical and cosmetic formulations, "green" extracts were prepared by employing "eco-friendly" extraction protocols as maceration, infusion and SLDE-Naviglio extraction. Metabolite profiles of the extracts were obtained by 1H NMR experiments and data were processed by multivariate statistical analysis to highlight differences in the extracts and to evidence the extracts with the highest concentrations of bioactive metabolites. Based on the NMR data, a total of 31 compounds were identified. The metabolite variation among the extracts was evaluated using Principle Component Analysis (PCA) and Partial Least Squares-Discriminant Analysis (PLS-DA). Furthermore, the total phenolic content of the extracts was measured by Folin-Ciocalteu colorimetric assay and the antioxidant activity of extracts was assayed by the spectrophotometric tests DPPH• and ABTS and by an in vitro test based on the evaluation of cellular reactive oxygen species production stimulated by pyocyanin.

Prunus dulcis leaves have been reported to exert some biological activity, in particular potent free radical-scavenging capacity, but so far there is limited information on their chemical composition. With the aim to achieve deep insight on the chemical constituents of the leaves of P. dulcis cultivars "Toritto" and "Avola", the most appreciated in Italy, an approach based on liquid chromatography-mass spectrometry (LC-MS) combined with isolation and structure elucidation of pure compounds by Nuclear Magnetic Resonance (NMR) analysis was carried out. Results allowed to detect in cv. Toritto leaves phenolics, terpenoids and a cyanogenic glycoside. Successively, various solvent systems were chosen to afford different extracts and an approach based on principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) from LC-MS data sets highlighted eco-friendly methods as selective in extracting phenolics and glycosides. Comparison of LC-MS profiles of the MeOH extracts of cv. Toritto and cvs. Avola (Pizzuta, Fascionello and Romana) leaves and evaluation of their phenolic contents and antioxidant activity were also carried out.

Extracts of aerial part of Euphorbia characias were examined to check potential inhibitors for three selected enzymes involved in several metabolic disorders. Water and ethanol extracts from leaves and flowers showed in vitro inhibitory activity toward α-amylase, α-glucosidase, and xanthine oxidase. IC50 values were calculated for all the extracts and the ethanolic extracts were found to exert the best effect. In particular, for the α-glucosidase activity, the extracts resulted to be 100-fold more active than the standard inhibitor. The inhibition mode was investigated by Lineweaver-Burk plot analysis. E. characias extracts display different inhibition behaviors toward the three enzymes acting as uncompetitive, noncompetitive, and mixed-type inhibitors. Moreover, ethanolic extracts of E. characias showed no cytotoxic activity and exhibited antioxidant capacity in a cellular model. The LC-DAD metabolic profile was also performed and it showed that leaves and flowers extracts contain high levels of quercetin derivatives. The results suggest that E. characias could be a promising source of natural inhibitors of the enzymes involved in carbohydrate uptake disorders and oxidative stress.

The aim of this study was to perform a preliminary chemical and physical characterization of the Carignano wine, an Italian monovarietal red wine mainly produced in the south-west of Sardinia (Italy). Technological parameters (alcohol, reducing sugars, total and volatile acidity, and pH), organic acid content, CIE L*C* ab h° ab chromaticity coordinates , phenolic compound contents (with spectrophotometric assays and HPLC-DAD), nitrogen compounds (with HPLC-FLD) and antioxidant capacity assessed by FRAP and DPPH assays were evaluated in 14 samples (vintage 2013) and compared with 3 aged samples. Carignano wines showed a significant level of phenolic compounds (2023 ± 435 mg GAE/L) and a good in vitro antioxidant capacity (31.6 ± 5.2 mmol Fe 2+ /L and 10.0 ± 1.4 mmol TEAC/L, respectively). The content of total polyphenols correlated significantly (p

Plants produce a vast array of biomolecules with beneficial effects for human health. In this study, polyphenol and anthocyanin-rich extracts (PAE) from pigmented tubers of Solanum tuberosum L. varieties “Blue Star”, “Magenta Love”, and “Double Fun” in comparison with the more extensively studied “Vitelotte” were evaluated and compared for antiproliferative effects in human leukemia cells, and their phytochemical and genetic profiles were determined. In U937 cells, upon treatment with PAE, it was possible to reveal the expression of specific apoptotic players, such as caspase 8, 9, 3, and poly (ADP-ribose) polymerase (PARP), as well as the induction of monocyte and granulocyte differentiation. A liquid chromatography/electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) investigation revealed the presence of polyphenolic compounds in all the varieties of potatoes analyzed, among which caffeoyl and feruloyl quinic acid derivatives were the most abundant, as well as several acylated anthocyanins. Each pigmented variety was genotyped by DNA-based molecular markers, and flavonoid-related transcription factors were profiled in tubers in order to better characterize these outstanding resources and contribute to their exploitation in breeding. Interesting biological activities were observed for “Blue Star” and “Vitelotte” varieties with respect to the minor or no effect of the “Double Fun” variety.

A comparison between High-Performance Thin-Layer Chromatography (HPTLC) analysis and Liquid Chromatography High Resolution Mass Spectrometry (LC&ndash, HRMS), coupled with Principal Component Analysis (PCA) was carried out by performing a combined metabolomics study to discriminate Arbutus unedo (A. unedo) plants. For a rapid digital record of A. unedo extracts (leaves, yellow fruit, and red fruit collected in La Maddalena and Sassari, Sardinia), HPTLC was used. Data were then analysed by PCA with the results of the ability of this technique to discriminate samples. Similarly, extracts were acquired by non-targeted LC&ndash, HRMS followed by unsupervised PCA, and then by LC&ndash, HRMS (MS) to identify secondary metabolites involved in the differentiation of the samples. As a result, we demonstrated that HPTLC may be applied as a simple and reliable untargeted approach to rapidly discriminate extracts based on tissues and/or geographical origins, while LC&ndash, HRMS could be used to identify which metabolites are able to discriminate samples.

Ziziphus jujuba Mill. leaves are receiving a great attention for their ability to improve sleep, exerting beneficial effects for both the heart and the central nervous system. With the aim to obtain a comprehensive analysis of the specialised metabolites occurring in the leaves of Z. jujuba, a LC-ESI/(HR)Orbitrap/MS profile in negative ion mode of the methanol extract was carried out. The LC-MS profile guided the isolation of 42 compounds, of which the structures were elucidated by 1D and 2D-NMR experiments. Based on this approach, 2 previously unreported dammarane-type saponins have been characterized along with flavonoid derivatives, dammarane-type saponins and triterpenic acids. Dammarane-type saponins were tested for their cytotoxic activity against A549 and HeLa cancer cell lines. None of the tested compounds, in a range of concentrations between 12.5 and 100 μM, caused a significant reduction of the cell number. This work provides a deep insight on the chemistry of the leaves of Z. jujuba and could be useful for further biological studies aimed at identifying phytochemicals contributing to the health benefits attributed to this herbal drug.

Corylus avellana (hazelnut) is one of the most popular tree nuts on a worldwide basis. The main products of C. avellana are kernels, a nutritious food, with a high content of healthy lipids, contained in a hard shell. In recent years, along with the ongoing research carried out on hazelnut kernels, a growing interest has been addressed to the hazelnut byproducts including hazelnut skin, hazelnut hard shell, and hazelnut green leafy cover as well as hazelnut tree leaf. These byproducts deriving from the roasting, cracking, shelling/hulling, and harvesting processes have been found as a source of “phytochemicals” with biological activity. The aim of this review is to provide a comprehensive and critical update on the chemistry and biological activity of specialized metabolites occurring in hazelnut kernels and byproducts. Phenolics are the most abundant phytochemicals not only in the kernels, but also in other processing byproducts. Attention has been also devoted to taxane derivatives isolated from C. avellana leaves. An overview on the biological activity, mainly antioxidant, antiproliferative, and antimicrobial along with less common biological effects, has been provided, contributing to highlight C. avellana as a source of bioactive phytochemicals with the potential to exert beneficial effects on human health. Finally, analytical techniques for the quali-quantitative analysis of specialized metabolites occurring in the different parts of C. avellana have been reviewed.

The species Myrtus communis L. represents a significant economic resource in Sardinia region (Italy), in fact its tissues are used both for the preparation of myrtle liquor and for essential oils or extracts with important pharmacological activities. Identification and quantification of polyphenolic compounds in leaves of M. communis L. appears interesting from both a biological and ecophysiological point of view. In the present study the discrimination of phytochemical content of M. communis L. leaves from different geographic origin and cultivars, was explored by Liquid Chromatography coupled with high resolution mass spectrometry (LC-ESI/LTQOrbitrap/MS) followed by Multivariate Data Analysis and phytochemical characterization. A total of 47 compounds were detected and 35 of them were tentatively identified on the bases of their retention time, UV/Vis spectra, MS spectra and MS fragmentation patterns. Principal Component Analysis (PCA) and Partial Least Square – Discriminant Analysis (PLS-DA) projection methods were applied to compare fingerprints and to discriminate the different geographical areas of the seeds used for the cultivation.

Introduction Prunus dulcis Mill. is a plant cultivated for the production of its edible seeds, known as sweet almonds. In the last decades almond demand has highly increased due to their wide use in the industrial manufacturing of almond-based foods; this has led to a huge production of waste materials, mainly corresponding to shells and husks. Objective To achieve a deeper understanding of the chemical composition of almond husks with the aim of exploring these byproducts as a source of bioactives to be used in nutraceutical and cosmetic formulations. Methods Methanol, ethanol and ethanol-water extracts of the almond husks were analysed by high-resolution liquid chromatography electrospray ionisation Orbitrap mass spectrometry (HR-LC-ESI-Orbitrap-MS) in negative ion mode. Tandem mass spectrometry (MS/MS) data were acquired by using the Data-Dependent Scan experiment, allowing the precursor ion to be selected as the most intense peak during LC-MS analyses. Nuclear magnetic resonance (NMR) experiments were performed on a Bruker DRX-600 spectrometer. Folin-Ciocalteu, DPPH• (2,2-diphenyl-1-picrylhydrazyl) and TEAC (Trolox equivalent antioxidant capacity) assays were employed to determine the total phenolic content and the radical scavenging activity of the extracts. Results The LC-MS/MS analysis of the methanol extract guided the isolation of phloroglucinol derivatives, flavonoids and terpenes. Eco-friendly extraction methods showed to be selective in extracting flavonoids while the comparison of the LC-MS profiles of the Italian cultivars Toritto and Avola showed significant differences, confirming how different growing conditions may influence the metabolome of a plant species. Conclusion This study led to a deeper insight into the chemical constituents of almond husks and showed how the eco-friendly extraction resulted in an effective method to obtain extracts rich in antioxidant sources.

The phytochemical content of Fragaria vesca L. (wild strawberry) grown in Campania Region (South Italy) was investigated. Wild and cultivated fruit were collected from different geographic areas and from bothautochthonous and non-autochthonous germplasm. Extracts were submitted to untargeted liquid chromatography coupled to high resolution mass spectrometry (LC–ESI-Orbitrap–MS) for metabolite profiling. 39 different phenolic compounds have been detected and identified in the methanolic extract of spontaneous and cultivated strawberries from different origins. Targeted quantitative analyses of selected known metabolites were performed using UHPLC interfaced to Q-Trap mass spectrometer in Multiple Reaction Monitoring mode. Principal Component Analysis (PCA) was applied to both untargeted and targeted results. PCA was applied to the untargeted profiling data indicating that fruits from locations with different pedoclimatic conditions can be discerned. Results from quantitative analysis indicate that autochthonous strawberries display significantly higher levels of anthocyanins, especially cyanidin 3-O-glucoside, and other phenolic compounds, like gallic acid and procyanidin B1, compared to the one from non-autochthonous germplasm. The targeted and untargeted metabolite profiling approach used in this work is proposed for the assessment of geographical origin of the berries. © 2016 Elsevier Ltd

Introduction Myrtus communis L. (Myrtaceae) is a self‐seeded shrub, widespread in Sardinia, with anti‐inflammatory, antiseptic, antimicrobial, hypoglycemic and balsamic properties. Its berries, employed for the production of sweet myrtle liqueur, are characterised by a high content of bioactive polyphenols, mainly anthocyanins. Anthocyanin composition is quite specific for vegetables/fruits and can be used as a fingerprint to determine the authenticity, geographical origin and quality of raw materials, products and extracts. Objective To rapidly analyse and determine anthocyanins in 17 samples of Myrtus communis berries by developing a platform based on the integration of UHPLC–MS/MS quantitative data and multivariate analysis with the aim of extracting the most information possible from the data. Methodology UHPLC‐ESI‐MS/MS methods, working in positive ion mode, were performed for the detection and determination of target compounds in multiple reaction monitoring (MRM) mode. Optimal chromatographic conditions were achieved using an XSelect HSS T3 column and a gradient elution with 0.1% formic acid in water and 0.1% formic acid in acetonitrile. Principal component analysis (PCA) was applied to the quantitative data to correlate and discriminate 17 geographical collections of Myrtus communis. Results The developed quantitative method was reliable, sensitive and specific and was successfully applied to the quantification of 17 anthocyanins. Peonidin‐3‐O‐glucoside was the most abundant compound in all the extracts investigated. Conclusion The developed methodology allows the identification of quali‐quantitative differences among M. communis samples and thus defines the quality and value of this raw material for marketed products. Moreover, the reported data have an immediate commercial value due to the current interest in developing antioxidant nutraceuticals from Mediterranean plants, including Sardinian Myrtus communis.

Juices obtained from cold-pressed saffron (Crocus sativus L.) floral by-products were evaluated as a potential source of compounds with antioxidant and cytotoxic activities. Floral by-products were split in two batches for extraction 24 and 48h after flower harvesting, respectively. The in vitro anti-oxidant activity of these extracts was tested using the FRAP and DPPH assays, and two biological models of lipid oxidation (activity in preventing cholesterol degradation and protection against Cu(2+)-mediated degradation of the liposomal unsaturated fatty acids). The cytotoxic activity was evaluated using the MTT assay. The results show that extracts obtained 48h post-harvest contained higher levels of total polar phenols and had the highest antioxidant activity in all of the performed assays. The LC-DAD and LC-ESI-(HR)MS(n) metabolic profiles showed high levels of kaempferol derivatives and anthocyanins. This study suggests that juices from saffron floral by-products could potentially be used to develop new products for the food and health industry.

The aim of the present study was to evaluate antioxidant, antimicrobial, anti-HIV, and cholinesterase inhibitory activities of aqueous and alcoholic extracts from leaves, stems, and flowers ofEuphorbia characias. The extracts showed a high antioxidant activity and were a good source of total polyphenols and flavonoids. Ethanolic extracts from leaves and flowers displayed the highest inhibitory activity against acetylcholinesterase and butyrylcholinesterase, showing potential properties against Alzheimer’s disease. Antimicrobial assay showed that leaves and flowers extracts were active against all Gram-positive bacteria tested. The ethanolic leaves extract appeared to have the strongest antibacterial activity againstBacillus cereuswith MIC value of 312.5 μg/mL followed byListeria monocytogenesandStaphylococcus aureusthat also exhibited good sensitivity with MIC values of 1250 μg/mL. Moreover, all the extracts possessed anti-HIV activity. The ethanolic flower extract was the most potent inhibitor of HIV-1 RT DNA polymerase RNA-dependent and Ribonuclease H with IC50values of 0.26 and 0.33 μg/mL, respectively. The LC-DAD metabolic profile showed that ethanolic leaves extract contains high levels of quercetin derivatives. This study suggests thatEuphorbia characiasextracts represent a good source of natural bioactive compounds which could be useful for pharmaceutical application as well as in food system for the prevention of the growth of food-borne bacteria and to extend the shelf-life of processed foods.

The health benefits of almonds along with their ability to prevent atheroschlerosis as well as cardiovascular and diabetes risks are well known. Previous works were focused mainly on the lipid fraction, thus a lack of information about the polar constituents still persists. In order to provide deeper insight into the chemical composition of almond, the polar fraction of Italian almond cultivars (Toritto and Avola) was investigated. The MeOH extract of the Toritto cultivar was submitted to LC-ESI-(HR)MS/MS experiments, highlighting the occurrence of several compounds, mainly cyanogenic glycosides, glycosylated flavonoids, proanthocyanidins, and a diterpene glycoside. EtOH and EtOH:H2O solution were also employed for extractions, resulting selective for flavonoids and proanthocyanidins, while cyanogenic glycosides were mainly detected in EtOH:H2O extract. Almonds were also blanched to afford skins and blanching water which were analyzed by LC-ESI-(HR)MS/MS experiments in order to establish the source of the identified compounds. Cyanogenic glycosides were detected in the peeled almonds, while flavonoids and proanthocyanidins were detected in almond skins and blanching water. The LC-ESI-(HR)MS/MS analyses of the almonds of the Avola cvs (Fascionello, Pizzuta and Romana) were compared with those of the Toritto cv., showing clear differences in their metabolome, probably due to the different growing conditions. Finally, total phenolic content and radical scavenging activity of the extracts and blanching waters were evaluated by Folin-Ciocalteu assay and by DPPH and ABTS+ assays, highlighting interesting antioxidant properties possessed by almond skins and blanching water, suggesting their potential employment in pharmaceutical, cosmetic and nutraceutical formulations.

Ziziphus jujuba Mill. leaves are receiving a great attention for their ability to improve sleep, exerting beneficial effects for both the heart and the central nervous system. With the aim to obtain a comprehensive analysis of the specialised metabolites occurring in the leaves of Z. jujuba, a LC-ESI/(HR)Orbitrap/MS profile in negative ion mode of the methanol extract was carried out. The LC-MS profile guided the isolation of 42 compounds, of which the structures were elucidated by 1D and 2D-NMR experiments. Based on this approach, 2 previously unreported dammarane-type saponins have been characterized along with flavonoid derivatives, dammarane-type saponins and triterpenic acids. Dammarane-type saponins were tested for their cytotoxic activity against A549 and HeLa cancer cell lines. None of the tested compounds, in a range of concentrations between 12.5 and 100 μM, caused a significant reduction of the cell number. This work provides a deep insight on the chemistry of the leaves of Z. jujuba and could be useful for further biological studies aimed at identifying phytochemicals contributing to the health benefits attributed to this herbal drug.

Extracts obtained from Pompia intrea (PI), a traditional candied fruit whose main ingredient is the pompia fruit (Citrus monstruosa L.) were evaluated for the first time. Volatile compounds were evaluated by headspace solid-phase microextraction (HS-SPME) followed by GC-FID/MS analyses. Polar compounds were identified by high-performance liquid chromatography coupled with electrospray mass spectrometry LC-ESI-Orbitrap-MS/MS and quantified by liquid chromatography coupled with ultraviolet/visible detection (LC-DAD). The antioxidant activity of these extracts was tested using the FRAP, CUPRAC, ABTS•+ and DPPH● assays. Moreover, their ability to protect intestinal cells against lipid peroxidation was studied. The HS-SPME GC-FID/MS confirmed the presence of typical molecules originating from the fruit (mainly terpenes, but particularly limonene). The LC-DAD and LC-ESI-(HR)MSn profiles showed high levels of neohesperidin (45.7 ± 11.1 mg/L) and 5-(hydroxymethyl)furfural (40.8 ± 23.5 mg/L). The results showed that the PI extracts contained high levels of total phenols and exhibited considerable antioxidant activity, which was significantly correlated to the presence of specific compounds such as neoeriocitrin and neohesperidin. Furthermore, pretreatments with different concentrations of PI extracts preserved enterocytes from oxidative damage by scavenging reactive oxygen species, thus counteracting lipid peroxidation. This study suggests that consumption of PI could provide intake of compounds with ascertained biological activity.

Oxidized white wines are produced by techniques that provide a barrel ageing which can range from a few years to some decades. This step, characterized by the metabolic activity of peculiar strains of Saccharomyces cerevisiae yeast, can affect the chemical composition of these wines and the production of unwanted substances such as biogenic amines. In this study, Vernaccia di Oristano wines from different vintages have been analysed for the first time regarding the content of biogenic amines and amino acids (by HPLC-FLD), and polar compounds (by HPLC-DAD and LC-MS). Furthermore, colour and technological parameters (contents of alcohol, reducing sugars, total and volatile acidities, pH and organic acids) of the wines were also evaluated. Older samples showed dark shades, which may have derived from polyphenols' oxidation while ageing. Some typical ageing products, such as 5-(hydroxymethyl)furfural and hydroxycinnamic acid derivatives were found in larger quantities in these samples, as well as the purinic compound xanthine, which was also detected in relevant concentrations. Additionally, as expected, the average of the main biogenic amines quantified in Vernaccia di Oristano was higher compared to non-oxidized white wines, especially in the older samples. Thus, though this content does not exceed values which spoil the quality of the wine, the monitoring of the winemaking conditions is suggested, to further limit the presence of these undesirable compounds.

Extracts of aerial part of Euphorbia characias were examined to check potential inhibitors for three selected enzymes involved in several metabolic disorders. Water and ethanol extracts from leaves and flowers showed in vitro inhibitory activity toward α-amylase, α-glucosidase, and xanthine oxidase. IC50 values were calculated for all the extracts and the ethanolic extracts were found to exert the best effect. In particular, for the α-glucosidase activity, the extracts resulted to be 100-fold more active than the standard inhibitor. The inhibition mode was investigated by Lineweaver-Burk plot analysis. E. characias extracts display different inhibition behaviors toward the three enzymes acting as uncompetitive, noncompetitive, and mixed-type inhibitors. Moreover, ethanolic extracts of E. characias showed no cytotoxic activity and exhibited antioxidant capacity in a cellular model. The LC-DAD metabolic profile was also performed and it showed that leaves and flowers extracts contain high levels of quercetin derivatives. The results suggest that E. characias could be a promising source of natural inhibitors of the enzymes involved in carbohydrate uptake disorders and oxidative stress.

Wild strawberry (Fragaria vesca) is recognized as a traditional food of Campania region (Italy). The vegetative parts have a pharmaceutical interest, being used as decoctions for hypertension treatment due their detoxifying, diuretic, stimulant and dermatological protective properties; leaves, that after collection of fruits are generally thrown away, could be an interesting byproduct, source of bioactive compounds for cosmetic and pharmaceutical industry. In the present work, the metabolite profiles of F. vesca leaves coming from populations spontaneously growing in the underwood (wild) and in crop (cultivated) and from autochthonous and non-autochthonous germplasm of Campania region (Italy) were investigated by LC-ESI/LTQOrbitrap/MS analysis. 27 metabolites mainly belonging to organic acids, flavonoids, catechin and its oligomers, and ellagitannins were putatively identified. Antioxidant activity was tested for each sample, in particular cultivated samples and wild samples with autochthonous germplasm of Campania region showed higher antioxidant activity compared to the non autochthonous ones. Moreover, in this study, it was possible to predict antioxidant metabolites, markers of this species, using LC-MS spectra and multivariate regression data analysis.

Ziziphus jujuba Mill fruits are recognized as an outstanding source of biologically active compounds including triterpenic acids. In order to evaluate the triterpenic profile of these edible and little commercial fruits and to contribute to the improvement of their potential value as food, a quali-quantitative study along with biological assays were carried out. The phytochemical investigation of the triterpenic fraction yielded nine triterpenic acids, ceanothic acid (1), alphitolic acid (2), maslinic acid (3), 3-O-cis-coumaroyl alphitolic acid (4), 3-O-trans-coumaroyl alphitolic acid (5), 3-O-trans-coumaroyl maslinic acid (6), 3-O-cis-coumaroyl maslinic acid (7), betulinic acid (8), and oleanolic acid (9). In order to perform the quantitative determination of compounds 1–9 in Z. jujuba fruits, an analytical method based on liquid chromatography coupled to mass spectrometry with ESI source and triple quadrupole analyzer (LC-ESI(QqQ)MS), using the very sensitive and selective mass tandem experiment called Multiple Reaction Monitoring (MRM), was developed and validated. Furthermore, the antiproliferative activity of compounds 1–9 was determined on three different cultured cell lines, namely J774A.1, MCF7 and A459 cells. For compounds 1, 2, 5 and 9, exhibiting no significant antiproliferative activity, the effects on nitrite production by LPS-stimulated J774.A1 cultured macrophages were evaluated (10–100 μM), showing the ability of alphitolic acid (2), and 3-O-trans-coumaroyl alphitolic acid (5) to reduce significantly (P

During last decades an increasing number of herbal products specifically targeting women's disorders has appeared in the worldwide marketplace. This growth highlights the need for a critical evaluation of quality, safety and efficacy of these products. Analytical techniques applied to the quality control of the main medicinal plants used for women health (relief of menopause and menstrual related symptoms) have been reviewed. Thanks to the innovation in analytical technology, identification and detection of secondary metabolites dramatically improved. In particular, hyphenated techniques have proved to be the most suitable for the rapid identification of compounds in plant matrix. Moreover, taking into account that differences in sample quality are not only found in the main compounds or in the chemical markers but also in the low-concentration compounds, fingerprint analysis might be a simple way for identification and quality control of herbal products containing a large number of low amounts of unknown compounds. Furthermore in several papers the informations obtained from the analysis of a plant have been processed by statistical elaborations. Medicinal plants here discussed are classified on the basis of the chemical markers used for their quality control.

Chemical investigations on Glycyrrhiza spp. have mostly been focused on G. glabra (typically cultivated in Europe, henceforth called European licorice), G. uralensis and G. inflata (known as Chinese licorice) with little information on the constituents of other Glycyrrhiza species. According to the growing interest in further Glycyrrhiza spp. to be used as sweeteners, the roots of G. triphylla have been investigated. The LC-ESI/LTQOrbitrap/MS profile of the methanolic extract of G. triphylla roots guided the isolation of 21 compounds, of which the structures were elucidated by 1D- and 2D-NMR experiments. Based on this approach, 6 previously unreported compounds including two isoflavones 7,5'-dihydroxy-6,3'-dimethoxy-isoflavone-7-O-β-d-glucopyranoside (4) and 7,5'-dihydroxy-6,3'-dimethoxy-isoflavone-7-O-(7,8-dihydro-p-hydroxycinnamoyl)-β-d-glucopyranoside (7) and four saponins, named licoricesaponins M3 (13), N2 (14), O2 (16) and P2 (18), have been characterized. It is to be noted that the accurate masses of some compounds here reported for the first time corresponded to those of compounds previously described in Glycyrrhiza spp. Thus an approach based only on MS analysis could be misleading; only isolation followed by NMR analysis allowed us to unambiguously assign the structures of these previously unreported compounds.

Moringa oleifera is a medicinal plant and an excellent dietary source of micronutrients (vitamins and minerals) and health-promoting phytochemicals (phenolic compounds, glucosinolates and isothiocyanates). Glucosinolates and isothiocyanates are known to possess anti-carcinogenic and antioxidant effects and have attracted great interest from both toxicological and pharmacological points of view, as they are able to induce phase 2 detoxification enzymes and to inhibit phase 1 activation enzymes. Phenolic compounds possess antioxidant properties and may exert a preventative effect in regards to the development of chronic degenerative diseases. The aim of this work was to assess the profile and the level of bioactive compounds in all parts of M. oleifera seedlings, by using different MS approaches. First, flow injection electrospray ionization mass spectrometry (FI-ESI-MS) fingerprinting techniques and chemometrics (PCA) were used to achieve the characterization of the different plant's organs in terms of profile of phenolic compounds and glucosinolates. Second, LC-MS and LC-MS/MS qualitative and quantitative methods were used for the identification and/or determination of phenolics and glucosinolates in M. oleifera.

Mulberries are consumed either freshly or as processed fruits and are traditionally used to tackle several diseases, especially type II diabetes. Here, we investigated the metabolite compositions of ripe fruits of both white (Morus alba) and black (Morus nigra) mulberries, using reversed-phase HPLC coupled to high resolution mass spectrometry (LC-MS), and related these to their in vitro antioxidant and α-glucosidase inhibitory activities. Based on accurate masses, fragmentation data, UV/Vis light absorbance spectra and retention times, 35 metabolites, mainly comprising phenolic compounds and amino sugar acids, were identified. While the antioxidant activity was highest in M. nigra, the α-glucosidase inhibitory activities were similar between species. Both bioactivities were mostly resistant to in vitro gastrointestinal digestion. To identify the bioactive compounds, we combined LC-MS with 96-well-format fractionation followed by testing the individual fractions for α-glucosidase inhibition, while compounds responsible for the antioxidant activity were identified using HPLC with an online antioxidant detection system. We thus determined iminosugars and phenolic compounds in both M. alba and M. nigra, and anthocyanins in M. nigra as being the key α-glucosidase inhibitors, while anthocyanins in M. nigra and both phenylpropanoids and flavonols in M. alba were identified as key antioxidants in their ripe berries.